EP0772648B2 - Utilisation d'une combinaison de stabilisants dans la production de feuilles de polychlorure de vinyle par calandrage - Google Patents

Utilisation d'une combinaison de stabilisants dans la production de feuilles de polychlorure de vinyle par calandrage Download PDF

Info

Publication number
EP0772648B2
EP0772648B2 EP95926891A EP95926891A EP0772648B2 EP 0772648 B2 EP0772648 B2 EP 0772648B2 EP 95926891 A EP95926891 A EP 95926891A EP 95926891 A EP95926891 A EP 95926891A EP 0772648 B2 EP0772648 B2 EP 0772648B2
Authority
EP
European Patent Office
Prior art keywords
weight
parts
polyvinyl chloride
carbon atoms
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95926891A
Other languages
German (de)
English (en)
Other versions
EP0772648B1 (fr
EP0772648A1 (fr
Inventor
Peter Wedl
Ernst-Udo Brand
Artur Peters
Jörg-Dieter KLAMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6524251&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0772648(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP0772648A1 publication Critical patent/EP0772648A1/fr
Publication of EP0772648B1 publication Critical patent/EP0772648B1/fr
Application granted granted Critical
Publication of EP0772648B2 publication Critical patent/EP0772648B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to the use of a stabilizer combination for molding compositions based on of polyvinyl chloride (PVC) in the production of semi-hard and soft polyvinyl chloride films after Calendering process to avoid the formation of deposits on the rollers used here.
  • PVC polyvinyl chloride
  • the term also includes both suspension, Bulk as well as emulsion polyvinyl chloride.
  • liquid Ba / Cdund commonly used for the production of semi-hard and soft PVC films Ba / Zn stabilizers sufficiently meet the requirements discussed above. Liquid Ca / Zn stabilizers do not lead to the formation of deposits on the calender rolls, but often only show insufficient ones Thermal and long-term stability.
  • DE-A-31 13 442 relates to stabilized PVC molding compositions which contain a stabilizer combination based on alkali, Alkaline earth and / or zinc soaps, costabilizers, finely divided crystalline water-containing alkali alumosilicates, lubricants as well as, if desired, further conventional additives. It is essential here that these stabilizer combinations in addition to an alkali alumosilicate, a costabilizer selected from ⁇ -diketones, ⁇ -ketoenol esters, Contain ⁇ -acyl lactones, substituted 1,4-dihydro-pyridinedicarboxylic acids and optionally substituted pyrroles. In a preferred embodiment, calcium soaps are also used together with zinc soaps.
  • EP-A-0 027 588 describes stabilizer combinations for PVC molding compositions which do the following Components contain: finely divided, crystalline, water-containing sodium aluminosilicates, calcium salts of fatty acids, Zinc salts of fatty acids, partial esters of fatty acids and polyols and thioglycolic acid esters of polyols and / or monofunctional alcohols.
  • DE-A-41 34 325 relates to a process for stabilizing polymers based on chlorine Olefins, using a stabilizer mixture which contains the following components: calcium complexes of 1,3-diketones, zinc and optionally calcium salts, ⁇ -diketones, hydrotalcites, sodium aluminosilicates and / or Calcium aluminum hydroxy phosphites, as well as polyols and / or hydroxyl group-containing isocyanurates.
  • the present invention relates to molding compositions based on polyvinyl chloride (PVC), with this term common homopolymers or copolymers of vinyl chloride and blends comprises such polyvinyl chloride compounds with other polymer compositions.
  • PVC polyvinyl chloride
  • Such polymers can be based on any ways, for example by suspension, emulsion or block polymerization.
  • their K value can range between about 65 and 80.
  • Polyvinyl chloride used preferably contains plasticizers in amounts of 10 to 100 parts by weight, in particular in amounts of 30 to 60 parts by weight, based in each case on 100 parts by weight of polyvinyl chloride.
  • the so-called “semi-hard” PVC films contain, for example, amounts of plasticizer in the range from 10 to 25 parts by weight, the so-called “Soft” PVC films plasticizer amounts in the range of 25 to 100 parts by weight, again related per 100 parts by weight of polyvinyl chloride.
  • the conventional plasticizers are used as plasticizers Plasticizer types described in the prior art in question - compare, for example, H. Kopsch, "Kalandertechnik", Carl Hanser Verlag (1978), pages 133 to 136.
  • the solid inorganic component (a) of the stabilizer combination to be used according to the invention are as described above, sodium aluminosilicates, hydrotalcites and basic calcium aluminum hydroxy phosphites in question. The following applies:
  • the synthetic, crystalline, finely divided sodium aluminosilicates containing 7 to 25% by weight of bound water mentioned under (a1) have - based on the anhydrous form - the formula (I): 0.7 to 1.1 Na 2 O.Al 2 O 3 .1.3 to 5 SiO 2
  • the synthetic crystalline sodium aluminosilicate thus defined is a zeolite known per se.
  • the general formula here includes both type A and type P zeolites; hence zeolite types, which differ only slightly in their chemical composition, in terms of their structure and properties differ significantly. To identify such types of zeolite, in addition to the chemical composition usually the X-ray diffraction pattern is used.
  • Type A zeolites can be characterized by the formula - based on the anhydrous form - 0.7 to 1.1 Na 2 O.Al 2 O 3 .1.3 to 2.4 SiO 2 characterize.
  • the zeolites A to be used according to the invention contain 13 to 25% by weight of bound water.
  • Preferred zeolites A within the scope of the present invention are those which have a water content in the range from 18 to 25% by weight.
  • those zeolites A are preferably used as component (a1) which have a particle size in the range from 0.1 to 20 ⁇ .
  • Such zeolites A can be produced by known methods, as are described, for example, in DE-B-24 12 837. Reference is also made to the disclosure of the publications mentioned below: DE-A-41 34 325, EP-A-0 027 588, DE-A-29 41 596 and DE-A-31 13 442.
  • Hydrotalcites of the formula (II) come as component (a2) Mg 1-x Al x (OH) 2 A x / n n- ⁇ mH 2 O in which 0 ⁇ x ⁇ 0.5, m denotes a positive number and A n - an anion with the valence 1, 2 or 3, in question, which may also be surface-modified.
  • hydrotalcites are also known compounds that can be prepared by various methods. With regard to the preparation of hydrotalcites to be used in accordance with the invention, reference may be made, for example, to the processes described in US Pat. Nos. 3,539,306, 3,650,704, 3,875,525 and DE-C-15 92 126 directed. Hydrotalcites of the general formula (II) in which A represents the carbonate anion are preferred. Also particularly preferred are hydrotalcites with a specific BET surface area of not more than 30 m 2 / g and in particular those which are sold under the trade name Alcamizer R by Kyowa Chemical Int.
  • the basic calcium aluminum hydroxy phosphites to be used according to the invention as component (a3) have the formula (III) Ca z Al 2 (OH) 2 (z + 2) HPO 3 .PH 2 O wherein z is a number in the range from 2 to 8 and p is a number in the range from 0 to 12.
  • These basic calcium aluminum hydroxy phosphites are also known. Their manufacture is described in DE-C-39 41 902. With regard to this class of compounds, reference is also made to the disclosure of DE-A-41 34 325.
  • hydrotalcites as well as the calcium aluminum hydroxy phosphites be modified on the surface, for example with surface-active substances, such as sodium stearate.
  • surface-modified compounds are best worked in aqueous suspension so that the Can absorb surfactants on the surface of the solid powder.
  • sodium alumosilicates of the zeolite type are preferred as component (a) A and / or hydrotalcite used. It is further preferred according to the invention, the components (a1) and / or (a2) alone or in a mixture in amounts of 0.3 to 2 parts by weight, based on 100 parts by weight of polyvinyl chloride, use.
  • Such zinc salts are known per se. As a rule, they are produced by precipitation of zinc salts with the corresponding carboxylic acids mentioned above or directly from zinc oxide and these carboxylic acids.
  • the following are examples of saturated, straight-chain monocarboxylic acids which are suitable for the purposes of the present invention: hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, dodecanoic acid ( lauric acid), tridecanoic, tetradecanoic (myristic), pentadecanoic, hexadecanoic (palmitic), heptadecanoic, octadecanoic (stearic), nonadecanoic, eicosanoic (arachidic) acid, heneicosanoic acid, docosanoic
  • the corresponding unsaturated and the corresponding branched monocarboxylic acids are also suitable for the zinc salts to be used according to the invention.
  • the substituted benzoic acids mentioned the p-tert in particular is an example here. Called butyl benzoic acid.
  • basic zinc salts of the type (ZnO) n Zn (monocarboxylic acid) 2 can also be used.
  • the basic zinc octoate is mentioned here as an example.
  • These basic zinc salts can also be used both alone and in a mixture with the zinc salts defined above.
  • saturated dicarboxylic acids are adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and the corresponding unsaturated dicarboxylic acids are also suitable here.
  • zinc salts are used as component (b) of saturated, straight-chain or branched monocarboxylic acids with 8 to 18 carbon atoms in amounts that are Ratio of zinc to component (a) such as 0.02 to 0.2 to 1, used.
  • the stabilizing effect of these consists of components (a) and (b) Stabilizer combination for the intended use according to the invention with regard to the required thermal stability values quite sufficient.
  • additional sliding or Release agent (c) the substances known from the prior art used for this purpose
  • Additional lubricants or release agents according to the invention the following types of compounds in question: homo- and / or copolymers of acrylate and / or methacrylate, oxidized polyethylene waxes, free fatty acids with 8 to 22 carbon atoms and their branched chain isomers, for example stearic acid or also hydroxystearic acid, ⁇ -olefins, wax esters, that is, esters of longer-chain monocarboxylic acids and monoalcohols, primary and secondary saturated and unsaturated higher alcohols with preferably 16 to 44 carbon atoms in the molecule, ethylenediamine distearate, montanic acid ester of Diols, for example of ethanediol, 1,3-butanediol and glycerol, mixtures of such montanic acid esters with unesterified montan acids, partial esters from
  • Examples for this are Mixed ester from maleic acid-pentaerythritol-behenic acid, mixed ester from adipic acid-pentaerythritol-oleic acid and mixed ester from adipic acid-pentaerythritol-stearic acid.
  • Such lubricants or release agents can be used in the sense of the present Invention both instead of and together with the aforementioned metal salts of calcium, Magnesium or aluminum can be used as an additional lubricant or release agent component (c).
  • the amount added is 0.05 to 1.5 parts by weight, based on 100 parts by weight of polyvinyl chloride.
  • the stabilizer combination according to the invention may also contain additional costabilizers.
  • additional costabilizers are also known from the relevant printed prior art.
  • the additional costabilizers to be used are preferably selected from ⁇ -diketones, organic phosphites, polyols, epoxidized oils, esters of epoxidized fatty acids with monoalcohols, calcium complexes of 1,3-diketones, thioglycolic acid esters of polyols or monofunctional alcohols and antioxidants.
  • costabilizers can also be used alone or as a mixture with one another.
  • the compositions reference is made to the relevant prior art. The following applies in detail following:
  • Suitable ⁇ -diketones for the purposes of the present invention are compounds known per se, for example in DE-B-27 28 865 or in DE-B-26 00 516 or in EP-B-0 063 180.
  • ⁇ -diketones are preferably selected from benzoylacetone, bis- (4-methylbenzoyl) methane, stearoylbenzoylmethane, Palmitoylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylmethane, benzoylacetyloctylmethane, dibutanoylmethane, Distearoylmethane, acetylacetone and stearolacetone.
  • Corresponding ⁇ -diketones are also described in DE-A-41 34 325 and disclosed in DE-A-31 13 442.
  • organic phosphites -Atoms such organic phosphites are disclosed, for example, in DE-A-41 34 325 and in DE-A-38 11 493. Commercially available solid phosphites can also be used as costabilizers according to the invention.
  • Suitable polyols for the purposes of the invention are those having 2 to 32 carbon atoms and 2 to 6 primary hydroxyl groups and / or isocyanurates containing hydroxyl groups.
  • Polyols selected from are preferred within the meaning of the invention Di-trimethylolpropane, dipentaerythritol and hydroxyl-containing isocyanurates.
  • Isocyanurates containing hydroxyl groups are also known compounds which are obtained by trimerization of hydroxyl-containing isocyanates Ring formation can be made. Of these, the tris (2-hydroxyethyl) isocyanurate is preferably used.
  • Epoxidized oils to be used for the purposes of the present invention are epoxides of esters of unsaturated, straight-chain fatty acids, for example epoxidized soybean oil, linseed oil, sunflower oil or tall oil, and alkyl epoxystearates.
  • the calcium complexes of 1,3-diketones to be used according to the invention are also known.
  • Appropriate Calcium complexes of 1,3-diketones are described, for example, in DE-C-27 16 389 and in DE-A-41 34 325 disclosed.
  • Suitable thioglycolic acid esters according to the invention are those of polyols having 2 to 6 carbon atoms and 2 to 6 Hydroxyl groups and / or those of monofunctional alcohols with 8 to 22 carbon atoms. Corresponding thioglycolic acid esters are disclosed, for example, in EP-A-0 027 588.
  • antioxidants suitable according to the invention in question for example 2,6-di-t-butyl-p-cresol, 2,5-di-t-butylhydroquinone, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, Diphenylolpropane, 2,5-bis (1,1-dimethylpropyl) hydroquinone, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane and ultraviolet absorbers such as 2-hydroxy-4-octoxybenzophenone and ethyl 2-cyano-3,3-diphenyl acrylate.
  • 2,6-di-t-butyl-p-cresol 2,5-di-t-butylhydroquinone
  • octadecyl 3- 3,5-di-t-butyl-4-hydroxyphenyl) propionate
  • Diphenylolpropane 2,5
  • the stabilizer combination according to the invention and any additional components to be added, which have been explained in detail above, are mixed into the PVC masses, for example under Use of ploughshare mixers, high-speed mixers, cocneting devices, pelletizing devices, Mixing rollers, extruders or intensive mixers, incorporated.
  • the stability of the PVC molding compound was checked on the basis of the static thermal stability of rolled skins.
  • PVC molding compositions containing the stabilizer combination were combined into one on a laboratory rolling mill Test head processed.
  • the test skins shredded into test pieces were then placed in a drying cabinet exposed to rotating hordes (Heraeus 6060) at a temperature of 190 ° C. Every 15 minutes Samples were taken and their color changes assessed; black discoloration means the respective one Stability end.
  • the roller coverings were assessed on a computer-controlled measuring roller mill (450 mm roller width x 252 mm roller diameter) in the following way: First, a rolled skin was placed on the front roller by task the mixture and mixed by hand for 3 minutes. The roll surface temperature was 185 ° C at the front, behind 175 ° C. After the mixture was homogenized on the rolling mill, an automatic driving program was started started in the following way: By changing the friction (40%) the rolled skin is moved from the front to the rear Rolled over. At a speed of 10 rpm. and a roll gap of 0.35 mm then became the deposit visually assessed on the chrome-plated roller. The chrome-plated, highly reflective rollers leave a precise statement regarding the formation of deposits. In a further step it was then assessed whether the rolled skin was light or difficult to lift off the roller.
  • a computer-controlled measuring roller mill 450 mm roller width x 252 mm roller diameter
  • DIDP plasticizer Diisodecyl phthalate stabilized with 0.3% by weight bisphenol A.
  • ESO Epoxidized soybean oil DPDP diphenylisodecyl Multicomponent ester Ester mixture of alcohols with 2 to 6 hydroxyl groups with aliphatic monocarboxylic acids with 12 to 30 C atoms and aliphatic dicarboxylic acids with 2 to 22 C atoms according to DE-C-19 07 768
  • BaZn stabilizer commercial liquid BaZn stabilizer zeolite Zeolite type A with 20% H 2 O according to EP-A-0 027 588 hydrotalcite commercially available hydrotalcite CHAP Calciumaluminiumhydroxyphosphit

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Claims (6)

  1. Utilisation d'une combinaison de stabilisateurs pour masses à mouler à base de chlorure de polyvinyle contenant :
    a) au moins un composant inorganique solide à des quantités de 0,3 à 3 parties en poids, par rapport à 100 parties en poids de chlorure de pplyvinyle, choisi parmi:
    a1) des aluminosilicates de sodium synthétiques cristallins fins contenant de 7 à 25 % en poids d'eau liée de formule (I) (forme anhydre) 0,7 à 1,1 Na2O.Al2O3.1,3 à 5 SiO2
    a2) les hydrotalcites de formule (II) Mg1-xAlx(OH)2Ax/n n-.mH2O dans laquelle 0<x<0,5, m est un nombre positif et An- un anion de valence 1, 2 ou 3, qui sont éventuellement modifiés à leur surface,
    a3) des hydroxyphosphites de calcium-aluminium basiques de formule (III) CazAl2(OH)2(z+2)HPO3.pH2O dans laquelle Z est un nombre compris entre 2 et 8 et p est un nombre compris entre 0 et 12,
    b) au moins un sel de zinc solide ou liquide à des quantités qui correspondent à un rapport du zinc au composant (a) tel que 0,02 à 0,25 pour 1, choisi parmi
    b1) les sels de zinc d'acides monocarboxyliques saturés ou insaturés, à chaíne droite ou ramifiée, avec 6 à 36 atomes de carbone,
    b2) les sels de zinc de l'acide benzoïque non substitué ou substitué par des radicaux alkyle en c1 à C4,
    b3) les sels de zinc d'acides dicarboxyliques saturés ou insaturés avec 6 à 10 atomes de carbone,
    c) un ou plusieurs composés choisis parmi
    c1) des sels de calcium d'acides monocarboxyliques saturés, à chaíne droite ayant de 16 à 22 atomes de carbone, à des quantités de 0,1 à 0,2 parties en poids par rapport à 100 parties en poids de chlorure de polyvinyle,
    c2) des sels de magnésium d'acides monocarboxyliques saturés, à chaíne droite ayant de 16 à 22 atomes de carbone à des quantités de 0,1 à 0,4 parties en poids par rapport à 100 parties en poids de chlorure de polyvinyle,
    dans la production de feuilles semi-dures et molles en chlorure de polyvinyle selon le procédé de calandrage pour éviter la formation d'un dépôt sur les cylindres employés dans l'opération.
  2. Utilisation selon la revendication 1,
    caractérisée en ce que
    le chlorure de polyvinyle utilisé contient des plastifiants à des quantités de 10 à 100 parties en poids, de préférence de 30 à 60 parties en poids, toujours par rapport à 100 parties en poids de chlorure de polyvinyle.
  3. Utilisation selon la revendication 1 ou 2,
    caractérisée en ce qu'
    on utilise comme composant (a) des aluminosilicates de sodium de type zéolithe A et/ou des hydrotalcites à des quantités de 0,3 à 2 parties en poids, par rapport à 100 parties en poids de chlorure de polyvinyle.
  4. Utilisation selon la revendication 1 ou 2,
    caractérisée en ce qu'
    on utilise comme composant (b) des sels de zinc d'acides monocarboxyliques saturés, à chaíne droite ou ramifiée, avec 8 à 18 atomes de carbone à des quantités qui correspondent à un rapport au zinc au composant (a) de 0,02 à 0,2 pour 1.
  5. Utilisation selon une ou plusieurs des revendications 1 à 4,
    caradtérisée en ce qu'
    on utilise comme agent lubrifiant ou de séparation supplémentaire (c) des polyacrylates, des cires de polyéthylène oxydées, des acides gras, du distéarate d'éthylène diamine, des esters d'acide montanique de diols, des esters partiels à base d'acide gras et de polyols, des esters mixtes ayant des indices d'hydroxyle ou d'acidité de 0 à 6 à base d'acides dicarboxyliques aliphatiques cycloaliphatiques, ou aromatiques ayant de 6 à 22 atomes de carbone dans la molécule, des polyols aliphatiques ayant de 2 à 6 groupes hydroxyle dans la molécule, et des acides monocarboxyliques aliphatiques ayant de 12 à 30 atomes de carbone dans la molécule, des esters de cire, des alcools à longue chaíne ou des α-oléfines.
  6. Utilisation selon une ou plusieurs des revendications 1 à 5,
    caractérisée en ce qu'
    on utilise des costabilisateurs supplémentaires qui sont de préférence choisis parmi les β-dicétones, les phosphites organiques, les polyols, les huiles époxydées, les complexes de calcium de 1,3-dicétones, les esters de l'acide thioglycolique de polyols ou les alcools monofonctionnels et les antioxydants.
EP95926891A 1994-07-27 1995-07-14 Utilisation d'une combinaison de stabilisants dans la production de feuilles de polychlorure de vinyle par calandrage Expired - Lifetime EP0772648B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4426571 1994-07-27
DE4426571A DE4426571A1 (de) 1994-07-27 1994-07-27 Verwendung einer Stabilisatorkombination bei der Herstellung von Folien aus Polyvinylchlorid nach dem Kalandrierverfahren
PCT/EP1995/002776 WO1996003459A1 (fr) 1994-07-27 1995-07-14 Utilisation d'une combinaison de stabilisants dans la production de feuilles de polychlorure de vinyle par calandrage

Publications (3)

Publication Number Publication Date
EP0772648A1 EP0772648A1 (fr) 1997-05-14
EP0772648B1 EP0772648B1 (fr) 1998-10-07
EP0772648B2 true EP0772648B2 (fr) 2002-05-22

Family

ID=6524251

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95926891A Expired - Lifetime EP0772648B2 (fr) 1994-07-27 1995-07-14 Utilisation d'une combinaison de stabilisants dans la production de feuilles de polychlorure de vinyle par calandrage

Country Status (6)

Country Link
US (1) US6140401A (fr)
EP (1) EP0772648B2 (fr)
CA (1) CA2196098A1 (fr)
DE (2) DE4426571A1 (fr)
ES (1) ES2122664T5 (fr)
WO (1) WO1996003459A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1803767A1 (fr) 2005-12-21 2007-07-04 Georg Fischer DEKA GmbH Composition de polymère thermopolastique, utilisable dans les MILIEUX REACTIFS

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW572965B (en) * 2000-08-04 2004-01-21 Sued Chemie Ag Use of amphiphilic polymers or copolymers for the surface modification of reactive inorganic fillers
PH12018502728B1 (en) * 2016-07-14 2022-10-21 Sakai Chemical Industry Co Chlorine-containing resin composition
CN118994733B (zh) * 2024-10-17 2025-08-19 浙江海利得新材料股份有限公司 一种糊浆用粉体钙锌稳定剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA979575A (en) † 1971-06-04 1975-12-09 Grace (W. R.) And Co. Thermal and light stabilized polyvinyl
FR2574805A1 (fr) † 1984-12-19 1986-06-20 Rhone Poulenc Spec Chim Procede de stabilisation de polymeres a base de chlorure de vinyle, compositions stabilisantes pour la mise en oeuvre du procede et polymeres ainsi stabilises
JPH04359946A (ja) † 1991-06-06 1992-12-14 Akishima Kagaku Kogyo Kk 熱安定性及び透明性を改善した食品包装フイルム用塩素含有樹脂組成物

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3539306A (en) * 1966-07-25 1970-11-10 Kyowa Chem Ind Co Ltd Process for the preparation of hydrotalcite
AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
FI58652C (fi) * 1973-04-13 1983-05-09 Henkel Kgaa Foerfarande foer tvaettning eller blekning av textilier samt medel foer genomfoerande av foerfarandet
US3875525A (en) * 1973-09-24 1975-04-01 Harmon Industries Digital automatic oscillator tuning circuit
GB1511621A (en) * 1975-01-10 1978-05-24 Rhone Poulenc Ind Stabilised vinyl chloride polymer compositions
MX4810E (es) * 1976-06-28 1982-10-15 Rhone Poulenc Ind Composicion mejorada estabilizada de policloruro de vinilo
NL168246C (nl) * 1976-08-02 1982-03-16 Seikisui Chemical Co Ltd Werkwijze voor de bereiding van een chloor-houdend harsmateriaal en gevormde voortbrengselen, vervaardigd onder toepassing van het aldus bereide chloor-houdende harsmateriaal.
DE2941596C2 (de) * 1979-10-13 1987-04-09 Neynaber Chemie Gmbh, 2854 Loxstedt Verfahren zur Stabilisierung von Polyvinylchloridformmassen und Mittel zur Durchführung des Verfahrens
US4338226A (en) * 1979-10-13 1982-07-06 Neynaber Chemie Gmbh Process for the stabilization of polyvinyl chloride and stabilizer compositions
HU191806B (en) * 1979-10-13 1987-04-28 Neynaber Chemie Gmbh Process for stabilyzing poly(vinyl chloride) forming masses and stabilyzing agent suitable for the process
JPS5836012B2 (ja) * 1980-11-07 1983-08-06 アデカ・ア−ガス化学株式会社 含ハロゲン樹脂組成物
DE3113442A1 (de) * 1981-04-03 1982-10-21 Henkel KGaA, 4000 Düsseldorf "stabilisierte polyvinylchlorid-formmassen"
JPH0639560B2 (ja) * 1986-08-14 1994-05-25 協和化学工業株式会社 ポリ塩化ビニル系樹脂の安定化組成物
DE3811493A1 (de) * 1988-04-06 1989-10-19 Neynaber Chemie Gmbh Stabilisator fuer polymerisate auf basis chlorhaltiger olefine, verfahren zu seiner herstellung und diesen enthaltende polymerisate
DE3923462A1 (de) * 1989-07-15 1991-01-24 Knauf Westdeutsche Gips Verfahren zur herstellung von kubischen na-p(pfeil abwaerts)c(pfeil abwaerts)-zeolith aus abfallstoffen von verbrennungsanlagen
JP2581814B2 (ja) * 1989-11-16 1997-02-12 協和化学工業株式会社 安定化された含ハロゲン樹脂組成物
DE3941902C1 (fr) * 1989-12-19 1991-02-28 Chemische Werke Muenchen Otto Baerlocher Gmbh, 8000 Muenchen, De
FR2661182B1 (fr) * 1990-04-20 1992-07-03 Rhone Poulenc Chimie Compositions stabilisees de polymere halogene.
DE4134325C2 (de) * 1991-10-17 1997-12-18 Henkel Kgaa Verfahren zur Stabilisierung von Polymerisaten des Vinylchlorids und Mittel zur Durchführung des Verfahrens
GB9216386D0 (en) * 1992-07-31 1992-09-16 Unilever Plc Use of aluminosilicates of the zeolite p type as low temperature calcium binders
US5352723A (en) * 1992-09-15 1994-10-04 Synthetic Products Company Stabilized vinyl halide compositions containing hydrotalcites
DE4238567A1 (de) * 1992-11-16 1994-05-19 Henkel Kgaa Stabilisatormischungen für Polymerisate mit Granaten
DE59405937D1 (de) * 1993-04-16 1998-06-18 Ciba Geigy Ag Stabilisiertes Polyvinylchlorid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA979575A (en) † 1971-06-04 1975-12-09 Grace (W. R.) And Co. Thermal and light stabilized polyvinyl
FR2574805A1 (fr) † 1984-12-19 1986-06-20 Rhone Poulenc Spec Chim Procede de stabilisation de polymeres a base de chlorure de vinyle, compositions stabilisantes pour la mise en oeuvre du procede et polymeres ainsi stabilises
JPH04359946A (ja) † 1991-06-06 1992-12-14 Akishima Kagaku Kogyo Kk 熱安定性及び透明性を改善した食品包装フイルム用塩素含有樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1803767A1 (fr) 2005-12-21 2007-07-04 Georg Fischer DEKA GmbH Composition de polymère thermopolastique, utilisable dans les MILIEUX REACTIFS

Also Published As

Publication number Publication date
DE59503867D1 (de) 1998-11-12
ES2122664T5 (es) 2002-12-01
WO1996003459A1 (fr) 1996-02-08
EP0772648B1 (fr) 1998-10-07
CA2196098A1 (fr) 1996-02-08
US6140401A (en) 2000-10-31
EP0772648A1 (fr) 1997-05-14
ES2122664T3 (es) 1998-12-16
DE4426571A1 (de) 1996-02-01

Similar Documents

Publication Publication Date Title
EP0062813B1 (fr) Masses moulées de chlorure de polyvinyl stabilisé
DE4002988C2 (fr)
EP0051788B1 (fr) Composition stabilisante pour résines thermoplastiques, en particulier pour polymères à base de chlorure de vinyle, et un procédé pour le façonnage à chaud de ces polymères
EP1088032B1 (fr) Association de stabilisants pour composition de resine thermoplastique halogenee
EP0422335B1 (fr) Masse de moulage sans plastifiant à base de chlorure de vinyle
DE2840875A1 (de) Aethylenpolymerfolie und das verfahren zu ihrer herstellung
DE2233743A1 (de) Stabilisiertes polyvinylchlorid und stabilisierungsmischungen hierfuer
WO1992015545A1 (fr) Dicarboxylates basiques d&#39;hydroxyde d&#39;aluminium et de calcium, leur procede de production et leur utilisation
DE19627258C2 (de) Verfahren zur Herstellung einer schmelzbaren Stabilisatorkombination
DE2540655A1 (de) Antistatische thermoplastische formmassen und formkoerper
WO1992006135A1 (fr) Composes laminaires cationiques
EP0586446B1 (fr) Composes stratifies cationiques modifies par des polymeres
DE3786597T2 (de) Polyvinylchlorid-Formmassepulver.
EP0772648B2 (fr) Utilisation d&#39;une combinaison de stabilisants dans la production de feuilles de polychlorure de vinyle par calandrage
DE2817452C2 (de) Stabilisatorzusammensetzung für Vinylchloridharze
DE1569009C3 (de) Stabilisierungsmittel fur Vinylhalogenidpolymerisate
DE2523909A1 (de) Physiologisch unbedenkliche stabilisatorkombinationen fuer halogenierte polyolefine
DE4103881C1 (fr)
DE19860798B4 (de) Zusammensetzung, enthaltend mindestens ein halogenhaltiges Polymer und einen Stabilisator sowie Verwendung einer röntgenamorphen Mischung
AT524902A1 (de) Verfahren zur Herstellung einer Stabilisatorzusammensetzung für ein Polymer und damit hergestellte Stabilisatorzusammensetzung
DE69633955T2 (de) Stabilisator für chlorhaltige Polymere, Verfahren zu deren Herstellung und chlorhaltige Polymerzusammensetzung
DE102010020263A1 (de) Zinnfreie Stabilisatorzusammensetzung
DE102010033203B3 (de) Stabilisatorzusammensetzung enthaltend organische 2-hydroxyethyl-substituierte Stickstoffverbindungen sowie Verwendung der Stabilisatorzusammensetzung
DE102004007429A1 (de) Granulare Stabilisatorzusammensetzungen für halogenhaltige Polymere und deren Herstellung
EP1171521B1 (fr) Combinaison de stabilisants pour compositions de resines thermoplastiques halogenees

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970120

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB GR IE IT LI NL SE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KLAMANN, JOERG-DIETER

Inventor name: PETERS, ARTUR

Inventor name: BRAND, ERNST-UDO

Inventor name: WEDL, PETER

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19971118

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB GR IE IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981007

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59503867

Country of ref document: DE

Date of ref document: 19981112

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2122664

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19981126

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990820

26 Opposition filed

Opponent name: AKZO NOBEL N.V.

Effective date: 19990624

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: COGNIS DEUTSCHLAND GMBH

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: COGNIS DEUTSCHLAND GMBH

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20020522

NLR2 Nl: decision of opposition
REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20020809

ET3 Fr: translation filed ** decision concerning opposition
REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN TRANSFER-

NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20020402793

Country of ref document: GR

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

GBTA Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977)
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20020723

Kind code of ref document: T5

NLS Nl: assignments of ep-patents

Owner name: COGNIS DEUTSCHLAND GMBH & CO. KG

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050714

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050714

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050715

Year of fee payment: 11

Ref country code: CH

Payment date: 20050715

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20050719

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20050721

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20050728

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20050805

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20050810

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050830

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070201

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070201

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060714

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070330

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20060715

BERE Be: lapsed

Owner name: *COGNIS DEUTSCHLAND G.M.B.H. & CO. K.G.

Effective date: 20060731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060731